US2588428A - Complex amine products with dialkyl zinc dithiocarbamates as pesticides - Google Patents

Complex amine products with dialkyl zinc dithiocarbamates as pesticides Download PDF

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US2588428A
US2588428A US586281A US58628145A US2588428A US 2588428 A US2588428 A US 2588428A US 586281 A US586281 A US 586281A US 58628145 A US58628145 A US 58628145A US 2588428 A US2588428 A US 2588428A
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amine
zinc
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pesticides
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William D Stewart
John H Standen
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Goodrich Corp
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BF Goodrich Corp
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof

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  • .nature are preferred, particularly amines and diamines, such as butyl amine, hex- .ade'cyl amine, dimethyl amine, diamylwamine, ethylene diamine, hexadecyl propylene diamine,
  • This invention relates to pest control compositions and more particularly to compositions which are useful as bactericides, fungicides and insecticides.
  • This invention has for its general object the provision of new and useful compositions having the power of killing or repelling economically or physiologically harmful pests, such as bacteria,
  • compositions which either kill or repel such pests.
  • pesticidal compositions comprising as an essential active ingredient a reaction product of a zinc dithiocarbamate, and an amine having at least one active hydrogen in the amino group and especially .amines of an aliphatic nature.
  • the zinc dithiocarbamates with which amines I may be reacted to give the compounds which are useful according to this invention are those in which the dithiocarbamate radical contains a secondary or tertiary nitrogen group, the same resulting from the interaction of a primary or secondary amine and carbon bisulfide, in accordance with the equation:
  • R1 and R2 mayrepresent one organic group and hydrogen or two individual organic groups, such as two methyl groups, or to ether they may represent one bivalent group such as a pentamethylene group present in piperidene or an oxy diethylene group present in morpholine.
  • R1 and R2 will be aliphatic in nature including such representative groups as alkyl, alicyclic, aralkyl and the like.
  • the amine which is added to or combined with a zincdithiocarbamate may be any of the organic amines available having at least one hydrogen atom in theamino group, but amines of aliphatic the alkyl peridene, symmetrical dimethyl ethylene diamine, symmetrical diethyl triethylene diamine, and especially those having a cyclohexyl group and an alkyl group of no'more than'eight carbon atoms such as N-butyl cyclohexylamine, N-ethyl cyclohexylamine, N-methyl cyclohexylamine, and the like.
  • the term "amine as employed in the specification and claims is intended to include all the amines of the type indicated of which the preceding are merely examples.
  • the addition products which are preferred as pesticides are those products formed by the reaction of equimolecular portions of a zinc dithiocarbamate and an amine. Said addition products are prepared by bringingtogether the zinc dithiocarbamate and the amine, preferably in the presence of a reaction diluent such as water, alcohol, gasoline, and the like. i To speed up the reaction, the mixture may be heated, the
  • Example 11 Ten Calex qaznquefasciatas larvae five to six days old are placed in aqueous dispersions containing respectively 1 p. p. m. and p. p. m. .of the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate in duplicate sets which are then incubated for 16 hours at 29 C.
  • the dispersion containing 1 p. p. m. of the addition product killed 80% of the larvae; the dispersion containing 10 p. p. m. of the addition product killed 100% of the larvae.
  • Example III Bean foliage is dipped in a 0.5% aqueous dispersion of the 1:1 addition product of the ethylene diamine and zinc dimethyl dithiocarbamate and then placed in Petri dishes.
  • a known number of Japanese beetles are placed on the wet treated bean foliage in the Petri dishes and the dishes are covered. By this treatment all of the beetles are dead within 24 hours with no damage to the foliage.
  • Japanese beetles were immersed in the above 0.5% aqueous dispersion and placed on bean foliage in Petri dishes, there was no feeding and all of the beetles were dead within 24 hours.
  • these addition products can be successfully used as insecticides. They can also be used as a spray by dissolving them in a solvent which can be used as an insecticide carrier.
  • Other insecticide materials such as rotenone may be incorporated to produce a spray of general utility.
  • these addition products can be milled with talc or bentonite in the proper proportions to produce a dust which will be effective.
  • These materials can also be prepared as aerosols and be used with satisfactory results.
  • reaction products of amines and zinc dit iocarbamates are not limited in use to insecticides but also are very effective as fungicides.
  • the following examples illustrate their ability to prevent the growth of fungi and molds.
  • Example IV In an agar plate test to determine fungicidal activity, the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate is incorporated into Difco malt extract a ar, the treated agar is then poured into Petri dishes, and the agar nutrient is inoculated by spraying same with a spore suspension of Alternaria 307mm and others with a spore suspension of Sclerotinia fructicola by means of an atomizer. Bv this treatment it was found that when 1 part per million of the chemical was present none of the spores of either fun us germinated when incubated for 3 days at 21 C.
  • Example V 4 dimethyl dithiocarbamate is added in the proportion of 1 p. p. m. to spore suspensions of Alternaria solam' and Sclerotim'a fructicola each in a 1% orange juice solution containing 50,000 5 spores/ml. Small droplets of these mixtures are placed on microscopic slides and incubated at 21 C. in a moist chamber for 18 to 24 hours. On examination it is found that none of the spores germinated in the spore suspensions thus treated.
  • These addition products are also effective as fungicides for the treatment of cotton fabrics to prevent destruction of the fabric by "mildew which is the destruction of the cotton fibers by mold (fungi) and bacteria.
  • the molds microorganisms belonging to the family of plants known as thallophytic plants, are plants which derive their nourishment wholly, or almost wholly, from organic compounds.
  • the molds responsible for rotting are capable of converting the 0 carbon of the cotton cellulose into a readily assimilable food which can result in complete destruction of the cotton material.
  • This destruc- 'tion is exceedingly rapid under tropical conditions, for, if the fabric or cotton material is in 25 contact with the ground, there is complete destruction of the material in 5 to 7 davs.
  • the following example demonstrates the ability of these addition compounds to prevent mildew" destruction to cotton fabric.
  • Example VI Test pieces of cotton fabrics are dipped in a 1% aqueous dispersionof the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate and then buried with untreated test pieces in soil heavily infested with cellulose-decomposing microorganisms. After 21 days there is very little change in appearance or strength of the treated fabric, while the untreated test piece is virtually destroyed by mildew.
  • Example VII A concentration of 1 p. p. m. of the 1:1 addition product of ethylene diamine and zinc dimethyl dithiocarbamate is added to spore suspensions of Alternaria solam' and Sclerotinz'a fructicola in orange juice solutions and tested as in Example V. After incubation in a moist chamber for 18 to 24 hours at 21 0., none of the spores had germinated.
  • Example VIII The 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate was used as a bactericide over a wide range of concentrations to determine its killing power on Staphylococcas aureas, but only the lo er port on of the killing concentrations are given. 10 to 1.00
  • amines with zinc dithiocarbamates are not only useful in killing Mexican bean beetles, Japanese beetles and mosquito larvae, but they also may" be usedto kill or repel other insect pests such as codling moths, carpet beetles, confused flour beetle adults and larvae, flies, moths, ticks, fleas, and the like.
  • isobutylundecylenam-ide and others. These mixtures may alsobe diluted with inert ingredients such as talc, calcium carbonate and tricalcium phosphate, or they may be dissolved or suspended in petroleum hydrocarbons, water, or alcohol. Dispersing, wetting and spreading agents such as lauryl alcohol, long-chain alcohol sulfates, sulfated and sulfonated alcohols, sodium salts of sulfated alcohols, sulfonated aliphatic derivatives, sulfonated aromatic and alkylaryl derivatives, hexahydric alcohol, esters of fatty acids, pine oils, and soybean lecithin may be used to aid in stabilizing the suspensions. Adhesives or sticking agents such as milk products, flour, gelatine and fish oils may be incorporated into the mixture to increase the retention or tenacity of spray deposits.
  • these addition products in solutions, dispersions or dusts, they may be used as agents for protecting plant and animal products such as wool, fur, silk, wood and other cellulosic materials, regenerated cellulose, cotton, leather, glue, paper, and plant latices from harmful pests, especially molds (fungi), insects and bacteria While the material to be protected is a raw ma- 3 terial or a finished product.
  • the solvents, dusts and aqueous suspensions generally used for convenience of application of pesticides have the common property of permitting projection of the materials through suitable jets or nozzles onto the materials to be treated, and will be designated in the appended claims for convenience, as fluent carriers.
  • a method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with the addition product of an aliphatic substituted zinc dithoicarbamate and an amine having at least one hydrogen atom in the amino group.
  • a method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with the addition product of an alkyl substituted zinc dithiocarbamate and an amine having at least one hydrogen atom in the amino group.
  • a method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with the addition product of a dialkyl substituted zinc dithiocarbamate and an amine having at least one hydrogen atom in the amino group.
  • a method of protecting materialscapabl'eof nourishing bacteria, fungi and insects from destruction by said'pests which comprises bringing the material into contact with the addition product of zinc dimethyl dithiocarbamate and an amine having at least one hydrogen atom in the amino group.
  • a method'of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with a mixture of a fluent carrier and a small proportion of the addition product of zinc dimethyl dithiocarbamate and ethylene diamine.
  • a method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with a mixture of a fluent carrier and a small proportion of the addition product of zinc dimethyl dithiocarbamate and cyclohexyl amine.
  • a pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of the Zinc salt of an N-aliphatic substituted dithiocarbamic acid with an amine in which each amino group contains at least one hydrogen atom.
  • a pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of the zinc salt of an N-alkyl substituted dithiocarbamic acid with an amine in which each amino group contains at least one hydrogen atom.
  • a pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active in redient being the product of the chemical addition of the zinc salt of an N-dialkyl substituted dithiocarbamic acid with an amine in which each amino group contains at least one hydrogen atom.
  • a pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of zinc dimethyl dithiocarbamate with an amine in which each amino group contains at least one hydrogen atom.
  • a pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wettng agent and the active ingredient being the product of the chemical addition of zinc dimethyl dithiocarbamate with ethylene diamine.
  • a pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of zinc dimethyl dithiocarbamate with cyclohexylamine.
  • a pesticidal composition comprising an active ingredient and a finely-divided solid carrier, the active ingredient being the product of the chemical addition of a zinc salt of an N-aliphatic substituted dithiocarbamic acid with an amine 7 having at least one hydrogen atom in the amino group.
  • composition according to claim 13 wherein the active ingredient is the addition product of zinc dimethyl dithiocarbamate and cyclohexyl amine.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

.nature are preferred, particularly amines and diamines, such as butyl amine, hex- .ade'cyl amine, dimethyl amine, diamylwamine, ethylene diamine, hexadecyl propylene diamine,
dlbutyl ethylene diamine, cyclohexylamine, piparison with .otherpesticides are given in detail.
Patented Mar. 11, 1952 COMPLEX AMINE PRODUCTS WITH DI- ALKYL ZINODITHIOCARBAMATES AS PESTICIDES William D. Stewart and John H. Standen, Yon kers, N. Y., assignors to The B. F. Goodrich Company, New York, N. Y.-, a corporation of New York N Drawing. Application April 2, 1945, Serial No. 586,281
14 Claims.
This invention relates to pest control compositions and more particularly to compositions which are useful as bactericides, fungicides and insecticides.
This invention has for its general object the provision of new and useful compositions having the power of killing or repelling economically or physiologically harmful pests, such as bacteria,
' compositions which either kill or repel such pests.
Other objects will appear hereinafter.
These objects are accomplished by the following invention of pesticidal compositions comprising as an essential active ingredient a reaction product of a zinc dithiocarbamate, and an amine having at least one active hydrogen in the amino group and especially .amines of an aliphatic nature.
The zinc dithiocarbamates with which amines I may be reacted to give the compounds which are useful according to this invention are those in which the dithiocarbamate radical contains a secondary or tertiary nitrogen group, the same resulting from the interaction of a primary or secondary amine and carbon bisulfide, in accordance with the equation:
. a metallicradical or the equivalent being present during the reaction to yield the acid in the form of its salt. R1 and R2 mayrepresent one organic group and hydrogen or two individual organic groups, such as two methyl groups, or to ether they may represent one bivalent group such as a pentamethylene group present in piperidene or an oxy diethylene group present in morpholine. Preferably, R1 and R2 will be aliphatic in nature including such representative groups as alkyl, alicyclic, aralkyl and the like.
The amine which is added to or combined with a zincdithiocarbamate may be any of the organic amines available having at least one hydrogen atom in theamino group, but amines of aliphatic the alkyl peridene, symmetrical dimethyl ethylene diamine, symmetrical diethyl triethylene diamine, and especially those having a cyclohexyl group and an alkyl group of no'more than'eight carbon atoms such as N-butyl cyclohexylamine, N-ethyl cyclohexylamine, N-methyl cyclohexylamine, and the like. The term "amine as employed in the specification and claimsis intended to include all the amines of the type indicated of which the preceding are merely examples.
The addition products which are preferred as pesticides are those products formed by the reaction of equimolecular portions of a zinc dithiocarbamate and an amine. Said addition products are prepared by bringingtogether the zinc dithiocarbamate and the amine, preferably in the presence of a reaction diluent such as water, alcohol, gasoline, and the like. i To speed up the reaction, the mixture may be heated, the
' boiling point of the common volatile solvents being a convenient temperature. The procedure for these reactions. is more fully described in the patents and in the literature which are concerned with the methods of preparing these addition products. One of the physical properties of these products which aids in their applicationas pesticides is their solubility in solvents or mixtures of solvents.
We have discovered that these addition products are highly efilcient fungicides and insecticides, being effective in aqueousdispers'ioii as dilute as 0.1 to 10 p. p. in. against Cutest-quinspecific zinc dithiocarbamate and amine addition products to bactericidal. fungicidal and-ins'ecticidal usesr These examples are intended to be illustrative andnotlimiting. In each test various amounts of the specific addition product were employed, but only'those tests which illustrate the. remarkable effectiveness of the mate- .r-ials or .the results which can be used for com- Example I Bean foliage is dipped in an 05% aqueous dispersion of the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate and then placed in Petri dishes. Mexican bean beetles and Japanese beetles are then placed on the treated foliage while wet in the Petri dishes, and the dishes are covered. By this treatment all the beetles are dead within 24 hours with no damage to the foliage.
Example 11 Ten Calex qaznquefasciatas larvae five to six days old are placed in aqueous dispersions containing respectively 1 p. p. m. and p. p. m. .of the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate in duplicate sets which are then incubated for 16 hours at 29 C. The dispersion containing 1 p. p. m. of the addition product killed 80% of the larvae; the dispersion containing 10 p. p. m. of the addition product killed 100% of the larvae.
Example III Bean foliage is dipped in a 0.5% aqueous dispersion of the 1:1 addition product of the ethylene diamine and zinc dimethyl dithiocarbamate and then placed in Petri dishes. A known number of Japanese beetles are placed on the wet treated bean foliage in the Petri dishes and the dishes are covered. By this treatment all of the beetles are dead within 24 hours with no damage to the foliage. When Japanese beetles were immersed in the above 0.5% aqueous dispersion and placed on bean foliage in Petri dishes, there was no feeding and all of the beetles were dead within 24 hours.
From these examples it is evident that these addition products can be successfully used as insecticides. They can also be used as a spray by dissolving them in a solvent which can be used as an insecticide carrier. Other insecticide materials such as rotenone may be incorporated to produce a spray of general utility. Where a dusttype insecticide is desired, these addition products can be milled with talc or bentonite in the proper proportions to produce a dust which will be effective. These materials can also be prepared as aerosols and be used with satisfactory results.
The reaction products of amines and zinc dit iocarbamates are not limited in use to insecticides but also are very effective as fungicides. The following examples illustrate their ability to prevent the growth of fungi and molds.
Example IV In an agar plate test to determine fungicidal activity, the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate is incorporated into Difco malt extract a ar, the treated agar is then poured into Petri dishes, and the agar nutrient is inoculated by spraying same with a spore suspension of Alternaria 307mm and others with a spore suspension of Sclerotinia fructicola by means of an atomizer. Bv this treatment it was found that when 1 part per million of the chemical was present none of the spores of either fun us germinated when incubated for 3 days at 21 C.
Example V 4 dimethyl dithiocarbamate is added in the proportion of 1 p. p. m. to spore suspensions of Alternaria solam' and Sclerotim'a fructicola each in a 1% orange juice solution containing 50,000 5 spores/ml. Small droplets of these mixtures are placed on microscopic slides and incubated at 21 C. in a moist chamber for 18 to 24 hours. On examination it is found that none of the spores germinated in the spore suspensions thus treated. These addition products are also effective as fungicides for the treatment of cotton fabrics to prevent destruction of the fabric by "mildew which is the destruction of the cotton fibers by mold (fungi) and bacteria. The molds, microorganisms belonging to the family of plants known as thallophytic plants, are plants which derive their nourishment wholly, or almost wholly, from organic compounds. The molds responsible for rotting are capable of converting the 0 carbon of the cotton cellulose into a readily assimilable food which can result in complete destruction of the cotton material. This destruc- 'tion is exceedingly rapid under tropical conditions, for, if the fabric or cotton material is in 25 contact with the ground, there is complete destruction of the material in 5 to 7 davs. The following example demonstrates the ability of these addition compounds to prevent mildew" destruction to cotton fabric.
Example VI Test pieces of cotton fabrics are dipped in a 1% aqueous dispersionof the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate and then buried with untreated test pieces in soil heavily infested with cellulose-decomposing microorganisms. After 21 days there is very little change in appearance or strength of the treated fabric, while the untreated test piece is virtually destroyed by mildew.
The 1:1 addition product of ethylene diamine and zinc dimethyl dithiocarbamate is equally effective against fungi. The following example illustrates its effectiveness in the spore suspension test.
Example VII A concentration of 1 p. p. m. of the 1:1 addition product of ethylene diamine and zinc dimethyl dithiocarbamate is added to spore suspensions of Alternaria solam' and Sclerotinz'a fructicola in orange juice solutions and tested as in Example V. After incubation in a moist chamber for 18 to 24 hours at 21 0., none of the spores had germinated.
These addition products are also effective bactei'lcides. Their ability to kill bacteria is illustrated in the following example.
Example VIII The 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate was used as a bactericide over a wide range of concentrations to determine its killing power on Staphylococcas aureas, but only the lo er port on of the killing concentrations are given. 10 to 1.00
p. p. m. of the 1:1 addition product of cyclohexylamine and zinc dimethyl dithiocarbamate are incorporated into 10 ml. portions of Difco 7 nutrient broth and 10% beef serum containing Staphylococcus aureus. After incubation at 40 C. for 24 hours, it is found that 10 p. p. m. is
sufficient to kill the bacteria in the broth, while 100 p. p. m. will kill the bacteria in the serum.'
The addition products of amines with zinc dithiocarbamates are not only useful in killing Mexican bean beetles, Japanese beetles and mosquito larvae, but they also may" be usedto kill or repel other insect pests such as codling moths, carpet beetles, confused flour beetle adults and larvae, flies, moths, ticks, fleas, and the like.
These addition products may be used. in combination with other active ingredients such as metallic arsenicals, fluosilicates, organic thiocyanates, phenothiazina. nicotine, pyrethruin,
isobutylundecylenam-ide, and others. These mixtures may alsobe diluted with inert ingredients such as talc, calcium carbonate and tricalcium phosphate, or they may be dissolved or suspended in petroleum hydrocarbons, water, or alcohol. Dispersing, wetting and spreading agents such as lauryl alcohol, long-chain alcohol sulfates, sulfated and sulfonated alcohols, sodium salts of sulfated alcohols, sulfonated aliphatic derivatives, sulfonated aromatic and alkylaryl derivatives, hexahydric alcohol, esters of fatty acids, pine oils, and soybean lecithin may be used to aid in stabilizing the suspensions. Adhesives or sticking agents such as milk products, flour, gelatine and fish oils may be incorporated into the mixture to increase the retention or tenacity of spray deposits.
By employing these addition products in solutions, dispersions or dusts, they may be used as agents for protecting plant and animal products such as wool, fur, silk, wood and other cellulosic materials, regenerated cellulose, cotton, leather, glue, paper, and plant latices from harmful pests, especially molds (fungi), insects and bacteria While the material to be protected is a raw ma- 3 terial or a finished product.
The solvents, dusts and aqueous suspensions generally used for convenience of application of pesticides, have the common property of permitting projection of the materials through suitable jets or nozzles onto the materials to be treated, and will be designated in the appended claims for convenience, as fluent carriers.
Since these addition products are not appreciably soluble in Water, leaching of the protective agent from fabrics that are treated with these addition products and subjected to all weather conditions is not a serious problem.
The above description and examples are intended to be illustrative only. Any modification of or variation therefrom which conforms to the spirit of the invention is intended to be included within the scope of the claims.
We claim:
1. A method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with the addition product of an aliphatic substituted zinc dithoicarbamate and an amine having at least one hydrogen atom in the amino group.
2. A method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with the addition product of an alkyl substituted zinc dithiocarbamate and an amine having at least one hydrogen atom in the amino group.
3. A method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with the addition product of a dialkyl substituted zinc dithiocarbamate and an amine having at least one hydrogen atom in the amino group.
4". A method of protecting materialscapabl'eof nourishing bacteria, fungi and insects from destruction by said'pests which comprises bringing the material into contact with the addition product of zinc dimethyl dithiocarbamate and an amine having at least one hydrogen atom in the amino group.
5. A method'of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with a mixture of a fluent carrier and a small proportion of the addition product of zinc dimethyl dithiocarbamate and ethylene diamine.
6. A method of protecting materials which are capable of nourishing bacteria, fungi and insects from destruction by said pests which comprises bringing the material into contact with a mixture of a fluent carrier and a small proportion of the addition product of zinc dimethyl dithiocarbamate and cyclohexyl amine.
7. A pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of the Zinc salt of an N-aliphatic substituted dithiocarbamic acid with an amine in which each amino group contains at least one hydrogen atom.
8. A pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of the zinc salt of an N-alkyl substituted dithiocarbamic acid with an amine in which each amino group contains at least one hydrogen atom.
9. A pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active in redient being the product of the chemical addition of the zinc salt of an N-dialkyl substituted dithiocarbamic acid with an amine in which each amino group contains at least one hydrogen atom.
10. A pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of zinc dimethyl dithiocarbamate with an amine in which each amino group contains at least one hydrogen atom.
11. A pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wettng agent and the active ingredient being the product of the chemical addition of zinc dimethyl dithiocarbamate with ethylene diamine.
12. A pesticidal composition essentially containing particles of an active ingredient dispersed in a fluent carrier, the carrier being an aqueous solution of a wetting agent and the active ingredient being the product of the chemical addition of zinc dimethyl dithiocarbamate with cyclohexylamine.
13. A pesticidal composition comprising an active ingredient and a finely-divided solid carrier, the active ingredient being the product of the chemical addition of a zinc salt of an N-aliphatic substituted dithiocarbamic acid with an amine 7 having at least one hydrogen atom in the amino group.
14. A composition according to claim 13 wherein the active ingredient is the addition product of zinc dimethyl dithiocarbamate and cyclohexyl amine.
WILLIAM D. STEWART. JOHN H. STANDEN.
REFERENCES CITED UNITED STATES PATENTS Name Date Tisdale et a1 Sept. 11, 1934 Number Number Name Date 2,243,544 ter Horst May 27, 1941 2,317,765 Hester Apr. 27, 1943 2,321,301 Lichty June 8, 1943 FOREIGN PATENTS Number Country Date 8103/32 Australia Apr. 24. 1933 OTHER REFERENCES Guy: Investigation of Organic Compounds as Insecticides, Bull. N0. 206, Technical No. 19, February 1937, University of Delaware Agri. Exp. Station, pp. 54-55, 167-22.

Claims (1)

1. A METHOD OF PROTECTING MATERIAL WHICH ARE CAPABLE OF NOURISHING BACTERIA, FUNGI AND INSECTS FROM DESTRUCTION BY SAID PESTS WHICH COMPRISES BRINGING THE MATERIAL INTO CONTACT WITH THE ADDITION PRODUCT OF AN ALIPHATIC SUBSTITUTED ZINC DITHOICARBOMATE AND AN AMINE HAVING AT LEAST ONE HYDROGEN ATOM IN THE AMINO GROUP.
US586281A 1945-04-02 1945-04-02 Complex amine products with dialkyl zinc dithiocarbamates as pesticides Expired - Lifetime US2588428A (en)

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US2768110A (en) * 1953-08-20 1956-10-23 Shell Dev Isothiourea compound fungicidal compositions and method of controlling fungi
US2805996A (en) * 1954-09-20 1957-09-10 Pennsalt Chemicals Corp Process for the production of oil soluble amine complexes and compositions containing such complexes
US2841522A (en) * 1954-05-20 1958-07-01 Pittsburgh Coke And Chemical C Fungicidal chloronitrobenzoic acid ester composition and method of using same
US2875834A (en) * 1951-12-29 1959-03-03 Monsanto Chemicals Zinc dithiocarbamate molluscacide
US2881071A (en) * 1957-07-12 1959-04-07 Buckman Labor Inc Processes for the control of slime-forming and other microorganisms and compositions for use therefor
US2881070A (en) * 1956-10-10 1959-04-07 Buckman Labor Inc Processes for the control of slime-forming and other microorganisms and compositionsfor use therefor
US2929758A (en) * 1957-09-23 1960-03-22 Buckman Labor Inc Processes for the control of iron bacteria and compositions for use therein
US2945752A (en) * 1956-03-08 1960-07-19 Dow Chemical Co Control of wild oats
US2951786A (en) * 1955-01-14 1960-09-06 Spencer Chem Co Bactericidal and fungicidal compositions comprising pentahalophenyl n-(phenyl) carbamates
US2977316A (en) * 1958-04-21 1961-03-28 Vanderbilt Co R T Bacteriostatic cleansing compositions
US3056822A (en) * 1958-09-22 1962-10-02 Monsanto Chemicals Bis(haloalkenyl)polymethylenebis-(dithiocarbamates)
US3096236A (en) * 1958-09-22 1963-07-02 Monsanto Chemicals Method for control of soil borne pathogenic organisms
US3098091A (en) * 1958-04-14 1963-07-16 Monsanto Chemicals Aminoalkyl esters of ether substituted dithiocarbamic acids
US3183189A (en) * 1961-03-20 1965-05-11 Commercial Solvents Corp Petroleum lubricants stabilized with bactericides
US3194825A (en) * 1962-04-19 1965-07-13 Union Carbide Corp (isothiocyanatoalkyl) amines
US3285921A (en) * 1961-11-30 1966-11-15 Bayer Ag Metal complexes of dithiocarbamates
US3379563A (en) * 1964-09-08 1968-04-23 Armour & Co Impregnated degradationresistant cloth
US3943143A (en) * 1973-04-30 1976-03-09 Pennwalt Corporation Oxazolidine and thiazolidine derived carbodithioate compositions useful as vulcanization accelerators
US3987017A (en) * 1974-02-01 1976-10-19 Pennwalt Corporation Process for the vulcanization of epdm elastomers
US20070060579A1 (en) * 2003-10-10 2007-03-15 Ulrike Wachendorff-Neumann Synergistic fungicidal active substance combinations
US20090018015A1 (en) * 2003-10-23 2009-01-15 Ulrike Wachendorff-Neumann Synergistic Fungicidal Active Combinations
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US1972961A (en) * 1931-05-26 1934-09-11 Du Pont Disinfectant
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AU810332A (en) * 1932-07-04 1933-05-04 E. I. du Pont de Nemours axd Co Improvements in or relating to disinfectants, fungicides bactericides andthe like
US2243544A (en) * 1939-04-12 1941-05-27 Us Rubber Co Composition of matter
US2321301A (en) * 1940-05-31 1943-06-08 Wingfoot Corp Composition of matter
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US2875834A (en) * 1951-12-29 1959-03-03 Monsanto Chemicals Zinc dithiocarbamate molluscacide
US2768110A (en) * 1953-08-20 1956-10-23 Shell Dev Isothiourea compound fungicidal compositions and method of controlling fungi
US2841522A (en) * 1954-05-20 1958-07-01 Pittsburgh Coke And Chemical C Fungicidal chloronitrobenzoic acid ester composition and method of using same
US2805996A (en) * 1954-09-20 1957-09-10 Pennsalt Chemicals Corp Process for the production of oil soluble amine complexes and compositions containing such complexes
US2951786A (en) * 1955-01-14 1960-09-06 Spencer Chem Co Bactericidal and fungicidal compositions comprising pentahalophenyl n-(phenyl) carbamates
US2945752A (en) * 1956-03-08 1960-07-19 Dow Chemical Co Control of wild oats
US2881070A (en) * 1956-10-10 1959-04-07 Buckman Labor Inc Processes for the control of slime-forming and other microorganisms and compositionsfor use therefor
US2881071A (en) * 1957-07-12 1959-04-07 Buckman Labor Inc Processes for the control of slime-forming and other microorganisms and compositions for use therefor
US2929758A (en) * 1957-09-23 1960-03-22 Buckman Labor Inc Processes for the control of iron bacteria and compositions for use therein
US3098091A (en) * 1958-04-14 1963-07-16 Monsanto Chemicals Aminoalkyl esters of ether substituted dithiocarbamic acids
US2977316A (en) * 1958-04-21 1961-03-28 Vanderbilt Co R T Bacteriostatic cleansing compositions
US3056822A (en) * 1958-09-22 1962-10-02 Monsanto Chemicals Bis(haloalkenyl)polymethylenebis-(dithiocarbamates)
US3096236A (en) * 1958-09-22 1963-07-02 Monsanto Chemicals Method for control of soil borne pathogenic organisms
US3183189A (en) * 1961-03-20 1965-05-11 Commercial Solvents Corp Petroleum lubricants stabilized with bactericides
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US3194825A (en) * 1962-04-19 1965-07-13 Union Carbide Corp (isothiocyanatoalkyl) amines
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US3987017A (en) * 1974-02-01 1976-10-19 Pennwalt Corporation Process for the vulcanization of epdm elastomers
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